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The Function of Cross Linker Carboxylic Acid for TiO2/Chitosan/SiO2

Coated as Self Cleaning Fabrics

Article  in  Oriental Journal of Chemistry · December 2018

DOI: 10.13005/ojc/340633

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 ISSN: 0970-020 X
ORIENTAL JOURNAL OF CHEMISTRY CODEN: OJCHEG
An International Open Access, Peer Reviewed Research Journal
2018, Vol. 34, No.(6):
Pg. 2942-2947
www.orientjchem.org

The Function of Cross Linker Carboxylic acid for

TiO2/Chitosan/SiO2 Coated as Self Cleaning Fabrics

YETRIA RILDA1*, SYUKRI1, DESI FERLINDA1, ANESSA IASA1,

ZULHADJRI1 and ANTHONI AGUSTIEN2

1
Department of Chemistry, Faculty of Mathematics and Natural Sciences, Andalas University, Indonesia.
2
Department of Biology, Faculty of Mathematics and Natural Sciences, Andalas University, Indonesia.
*Corresponding author E-mail: yetriarilda@yahoo.com, yetriarilda@sci.unand.ac.id

http://dx.doi.org/10.13005/ojc/340633

Received: October 29, 2018; Accepted: November 19, 2018)

ABSTRACT

The chemical compound TiO2/Chitosan/SiO2 is a photocatalyst with a self- cleaning capability

against dye contaminations. Morphologically, it has an anatase structure with 13.1 nm of crystallite
size, spherical shape, and Eg = 3.209 eV as characterized by X-ray diffraction, TEM, and UV-DRS.
The self-cleaning capability of TiO2/Chitosan/SiO2 against the malachite green dye spot was optimized
using two carboxylic acid cross-linkers namely 1,2,3,4- Buthane Tetra Carboxylic Acid (BTCA) and
Chloro Acetic Acid (CAA). The optimization in enhanced the growth of ester covalent interaction with
the functional groups of textile fiber was performed gradually in CAA and directly in BTCA to produce
a self-cleaning textile. The self-cleaning efficiency of cross-linker under the UV irradiation (536 lux for
60 min.) was 96% and 69.96% in CAA and BTCA, respectively. The FT-IR analysis revealed that the
ester covalent interaction among the cross-linker, cotton fiber, and TiO2/Chitosan/SiO2 nanocluster
could be determined by the intensity change of C=O stretching of the functional group at1700-1710
cm-1 . The intensity was higher in CAA (15.03%) than BTCA cross-link (12.04%). The superficial
morphological feature of the cotton fiber as observed by SEM depicted that TiO2/Chitosan/SiO2 particles
were dispersed more evenly in the CAA than BTCA. The TiO2/Chitosan/SiO2 nanocluster with a CAA
cross-link is reliable to be used indesigning a high-quality self-cleaning textile.

Keywords: Cross linker, BTCA, CAA, self-cleaning, Malachite green.

INTRODUCTION of cotton fiber makes it easy to be contaminated

Textile is cer tainly needed infashion
industries as well as various medical and office
equipments, and other daily needs. The cotton textile
is preferable as compared to the other materials due
to its ease of maintenance, the strength, absorption,
and affordability1. However, the higher absorption
by dirt and dyes, thus it is also difficult to be removed
out2. As an alternative solution, some researchers
modified the textile cotton fiber to acquire the
self-cleaning capability against the dye spots
contaminating the textile surface. The self- cleaning
textile is practically effective to shorten the contact
time of the dirt on the textile. Consequently, the dirt

This is an Open Access article licensed under a Creative Commons license: Attribution 4.0 International (CC- BY).
Published by Oriental Scientific Publishing Company © 2018
 RILDA et al., Orient. J. Chem., Vol. 34(6), 2942-2947 (2018)
could be easily cleaned and the deterioration of the
textile fiber could be maximally prevented3,4.
The nano-oxide metals including TiO2, ZnO
or its composites are commonly used in modifying the
cotton fiber due to their functional capability as the
sunscreen, self- cleaning agents and antimicrobes3-5.
The capabilities of the substances are related to their
pivotal role as photocatalysts. Hence, they could
remove the dye on the fiber by the photocatalytic
mechanism.The previous study by Wijesena, applied
this concept to develop the self-cleaning materials
by using the TiO2 and ZnO nanoparticles against
the dye spots of methyl orange4. Moreover, Pakdel
and Doud used TiO2 and SiO2 nanocomposites to
enhance the functional capability of self-cleaning
textile against various dyes including methyl
orange4,6,7, methylene blue3,8, disperse yellow and
C.I. reactive red9, and acid red10.
The coating of nano-oxide metal on the
cotton fiber basically requires the cross-link agent,
a carboxylic group-consisting compund, in order
to promote the covalent interaction with the fiber
cellulose and TiO2 by means the electro statics
interaction11. The stability of TiO2-SiO2 nanocluster’s
coating on the cotton fiber is determined by the type
of carboxylic acid used as the cross-linker. A study by
Karimi demonstrated that the use of succinate acid
as across-linker inthe TiO 2-SiO2 particle’s coating
could stand its stability up to 85% against washing,
while it was only 11% without a cross-linker5,11,12.
Furthermore, our previous study revealed
that acrylic acid is an effective cross-linker to
develop a textile acquiring the antimicrobe and
self-cleaning capability against methylene blue dye4.
Esrter covalent interaction
Fig. 1. Mechanism of ester covalent interaction among fiber
cellulose, TiO2/ Chitosan/SiO2/ nanocluster and BTCA cross-link
2943
Esrter covalent interaction
Fig. 2. Carboxymethylation mechanism of cellulose by
4
natrium mono- chloroacetic
In this present study, we used two cross-
linkers including 1,2,3,4 buthane tetra carboxylic
acid (BTCA) and chloroacetic acid (CAA) with two
different coating methods by means direct and
gradual coating, respectively. It aimed to enhance
the self-cleaning capability against the dye spot of
malachite green on a textile cotton fiber with a
densely TiO2/Chitosan/SiO2 coating.
EXPERIMENTAL
Materials
The instruments used in this study were
magnetic stirrer, furnace, oven, analytical balance,
spin coating machine, optic microscope, SEM-
EDX (Hitachi S-3400N), FT-IR (Thermo Scientific:
Nicolet iS10), XRD (X’Port PAN Analytical),
UV-Vis DRS (Shimadzu UV-Vis 2450), and TEM
(JEOL JEM 1400). The materials and chemicals
were silky textile cotton, hydrochloric acid (HCl,
Merck), acetic acid (CH3COOH, Merck), aquadest,
titanium isopropoxide (C12H28O4Ti) (Aldrich 97%),
diethanolamine(C4H11NO2) (Merck), isopropanol
(C3H8O, Merck), tetra ethyl ortho silicate (C 8H20O4Si,
Merck), chitosan (C 6H11NO4)n, 1,2,3,4-buthane
tetra carboxylic acid (C 8H 10O8, BTCA, Merck),
chloroacetic acid (C2H3O2Cl, CAA, Merck), ethyl
tri methyl ammonium bromide (C 13H33N(CH3)3Br,
Merck), detergent, natrium carbonate (Na2CO3),and
malachite green (C23H26N2Cl).
Methods
Synthesis of TiO2/Chitosan/SiO2 nano cluster
The powder of TiO2/Chitosan/SiO2
nanocluster was synthesized using a sol-gel
method with the titanium isopropoxide (TIP) and tetra
ethyl ortho silicate as precursors. The sol solution
consisted of A solution (TIP and DEA in isopropanol
solvent; 1:2:2 in M) and B solution (TEOS and HCL
2 M in isopropanol; 1:2:2). The A and B solution
 RILDA et al., Orient. J. Chem., Vol. 34(6), 2942-2947 (2018) 2944

was homogenized separately for 30 min. in RT.
The combination of A and B solution was prepared
as a mixed sol with a composition of Ti and Si 3:2.
Furthermore, the chitosan/acetic acid suspension
(1:20) and CTAB (1:5) were added to the sol. The
mixed sol was set at pH 10-11 and homogenized
for 8 h followed by the heating at 110-120oC or
15 h to produce a gel. The gel was then calcinated at
500oC for 3 h to obtain the powder of TiO2/Chitosan/
SiO2 nanocluster and subsequently morphologically
characterized using XRD, UV-Vis DRS, and TEM.
by the sol-gel synthesis method was identified
using XRD, UV-Vis DRS, and TEM to determine the
morphological characters related to its prospective
application as a self-cleaning material. It was found
that the nanocluster depicted ananatase structure
with 13.1 mm crystallite size at the highest intensity 2
θ
= 25.3o. The anatase intensity order of TiO2/Chitosan/
SiO2 was 2θ = 25.3o; 36.93o; and 48o as elucidated
by XRD analysis (Fig. 3). The crystallite size was
calculated by the Scherrer formula as follow:

Coating of textile cotton fiber D=

The textile cotton of size 64 m2 was firstly
washed using detergent 2 g/L and subsequently D (crystallite size), k (constant; 0.89)l,
rinsed with aquadest and dried up at 80 oC for (wavelength of X rays), b (value of full width at half
5 min. Furthermore, it was dewaxed using Na2CO3
maximum, FWHM), q and (diffraction angle)6,13,14.
0.01 g in 25 mL aquadest for 5 min. at 100 oC and
rinsed with aquadest to adjust the pH 6-7, followed
by heating at 80oC for 5 minute. The textile cotton The crystallite size could be modified
was directly soaked in 1 M BTCA cross-link for by adding the dopant of SiO 2 and chitosan. The
12 hours. In another treatment, the textile was firstly SiO2 functions to form the pores and to extend the
soaked into 2 M NaOH for 30 min. then into 1 M CAA. surface area15,16 while the chitosan plays a role as
After the treatment using BTCA and CAA, the textile a template of porosity during the condensation of
was heated at 80oC for 5 min. then coated using a the crystallite and enhances the SiO 2 dispersion
suspension of 1% TiO2/Chitosan/SiO2 by means on TiO2 surface16. It has been demonstrated that
dip-spin coating for 90 min. It was then dried up at when the TiO2 and SiO2 were composited, it could
80oC for 15 min. and subsequently analyzed using inhibit the structural transformation of anatase to rutile
FT-IR, Photo Optics, XRD, and SEM- EDX. phase15. Moreover, we have previously reported that
the distribution of crystallite size was affected by the
Self-cleaning test of the textile cotton fiber sol and gel preparation process18. The sol preparation
The self-cleaning test was carried out by for 8 h and gel polycondensation for 15 h noticeably
observing the degradation of the malachite green increased the distributional uniformity of crystallite size
dye spot on the coated cotton fiber under the of TiO2/chitosan/SiO2 nanocluster. The pattern of UV-
UV irradiation (536 lux) in 0-2 h time window. The 4x4 DRS spectrum of TiO2/chitosan/SiO2(presented in Fig.
cm textile dropped by 50 μL of 150 ppm malachite 3, left panel was thenconverted using Plank equation
green was designated for a qualitative test, while the [Eg = ] (Fig. 3, right panel) with Eg (band gap), h
1x1 cm textile soaked into 20 mL of 5 g/L malachite (Plank constant, 6.626 x 10-34 J.s), c (light speed, 3 x
green was used for a quantitative test. The textile 108 m.s-1) and (wavelength, in m). It wasrevealed that
sample was observed in the darkroom for 30 min. the maximum wavelength was 386.3 nm and the Eg
and the absorption was subsequently noted as Ao. was 3.209 eV. Hence, the photocatalytic reaction of the
Furthermore, it was irradiated by UV light in 0-2 h then TiO2/Chitosan/SiO2 could be induced by the UV light
the absorption was noted as A. The dye degradation (= 385 nm) with the energy equals the Eg value19.
rate (Ef) was calculated by the formula as follow:
The TEM pattern (Fig. 4) illustrates the
Ef : x100 %
3-dimensional feature of TiO2 hybridized with SiO2
and chitosan. It was found that the TiO2/Chitosan/
RESULTS AND DISCUSSION
SiO2 nanocluster has a spherical crystallite shapeand
Morphological characters of TiO2/Chitosan/SiO2 non-agglomerated structure. The SiO2 and chitosan
nanocluster were amorph, and SiO2 and TiO2 formed a core-shell
formation with the chitosan functioned as the cross-
The TiO2/Chitosan/SiO2 nanocluster yielded linker20. The TEM-derived picture, in consistent with
 RILDA et al., Orient. J. Chem., Vol. 34(6), 2942-2947 (2018)
the XRD spectral pattern,indicated that TiO2 has the
highest crystallite intensity at 2θ = 25.3o in anatase
phase.
Fig. 3. The XRD and UV-DRS spectral patterns of TiO2/
Chitosan/SiO2
Fig. 4. TEM of TiO2/chitosan/SiO2 (Ti : Si : (3:2) at (a) 50 nm
(b) 100 nm FT-IR analysis
The FT-IR analysis of the cotton fiber
coated by TiO2/Chitosan/SiO2 with two cross-linkers
(CAA and BTCA) produced the FT-IR spectrum as
presented in Fig. 5. The patterns ofthe spectrum
indicated that the intensity difference was observed
at 1710 cm-1 identified as the covalent ester
formation’s zone (C=O stretching)21. The CAA cross-
link has a higher intensity than BTCA, suggesting
that the gradual growing of ester group in CAA could
enhance the thickness of TiO2/Chitosan/SiO2 coating
on the fiber by means the electrostatic interaction8.
The FT-IR spectrum of the uncoated fiber
(Fig. 5a) depicted its absorbance at cm -1 with the
intensity 10.1%, while the coated fiber by CAA cross-
link (Fig. 5b) indicated the shifted wave number to
1710.04 cm-1 and the increased intensity to 15.03%.
Likewise, the coated fiber by BTCA cross-link
(Fig. 5c) also demonstrated the shifted wave number
to 1708.5 cm -1 and increased intensity to 12.4%.
The shiftings of the wave number indicated the
chemical esterification’sinteraction between the
cellulose of cotton fiber and the carboxylic cross-link
as illustrated in Figure 1.
The cotton fiber coated by TiO2/Chitosan/
SiO2 nanocluster with a CAA cross-link depicted the
2945
different FT-IR spectrum as compared with BTCA
cross-link. Interestingly, the absorbance intensity at
3400 cm -1 and 1529 cm -1 was also observed. The
occurrance of the absorbance intensity at 3400 cm -1
might be resulted from the combination of carboxylic
absorbance and alchoholic -OH stretchings’s
absorbance. The absorbance intensity at 1529 cm -1
was reported as an absorbance of the carboxylic
ionic group4.
Fig. 5. The FT-IR of cotton fiber in (a) uncoated (b) coated
with TiO2/chitosan/SiO 2, 1 M BTCA (c) coated with TiO2/
chitosan/SiO2, 1 M CAA
Morphological analysis using SEM-EDX
The morphological observation by using
SEM suggested the difference in the features of
cotton fiber treated with a CAA cross-link and BTCA
cross-link (Fig. 6a-c). A cross-link plays a pivotal role
in th formation of ester covalent interaction with the
hydroxyl group of fiber, thereby the coating of the
TiO2-SiO2 nanocluster on the textile. Meanwhile,
the chitosan in TiO2-SiO2 provides the nitrogen base
in order to enhance the amide covalent interaction
and thereby trapping the TiO2-SiO2 by means the
electrostatic interaction6. The difference in the cross-
link determines the distributional uniformity of the
TiO2/Chitosan/SiO2 nanoparticle on the textile fiber
surface. It was found that in the CAA cross-link-
treated fiber, the coating particles dispersed more
evenly and densely on the surface of the textile as
compared with the BTCA cross-link-treated fiber.
Chen et al., reported that cotton fiber coated
by TiO2 depicted the rough surface feature. The
roughness of the surface affects the self-cleaning
capability of the fiber22. The results of SEM analysis
(Fig. 6) and the pattern of EDX (Fig. 7), taken
together, suggested that the technique of the growing
an ester covalent interaction on the fiber determines
 RILDA et al., Orient. J. Chem., Vol. 34(6), 2942-2947 (2018)
the amount of TiO2-SiO2 coating, its distributional
uniformity as well as the stability of the coating.
Based on the EDX analysis, the composition of C,
O, Ti and Si elements was equal to the composition
of Ti and Si used as the precursors in the TiO2-SiO2
synthesis (3:2 in M). The elements found in the
cotton fiber coated by TiO 2/Chitosan/SiO2 with a
BTCA cross-link consisted of C = 27.6%, O = 17.97%,
Ti = 2.36 %, and Si 0.90 %. Otherwise, the elements
in the fiber with a CAA cross-link composed of
C = 50.73 %, O = 38.64 %, Ti = 2.46 %, and Si 1.45%.
Fig. 6. The SEM pattern and optical feature of cotton fiber
in (a) uncoated and (b) coated by TiO2/chitosan/SiO2 with a
BTCA cross-linkand(c) CAA cross-link
Fig. 7. The EDX pattern of cotton fiber coated by TiO 2/
chitosan/SiO2 (3 : 2) with (a) BTCA (b) CAA Cross link
Self-cleaning test
The self-cleaning capability of the cotton
fiber coated by TiO2/Chitosan/SiO2 nanocluster
against malachite green dye spot was evaluated both
qualitatively and quantitatively. The qualitative test
(Fig. 8) revealed that the cotton fiber coated by TiO2/
Chitosan/SiO2 with a CAA cross-link acquired the
capability to degrade the malachite green dye spot
five times stronger as compared with BTCA cross-
link. This result is in accordance with the findings
by FT-IR and SEM analysis demonstrating that the
CAA cross link noticeably elevated the abundance
of TiO2/Chitosan/SiO2 on the textile fiber.
2946
Fig. 8. Degradation of malachite green dye spot after UV
irradiation for 0-8 h on the cotton fiber with (a) uncoated
and (b) coated by TiO2/chitosan/SiO 2 with BTCA cross link
and (c) CAA cross-link
The quantitative test for the self-cleaning
capability of the cotton textile was conducted by
measuring the absorbance of malachite green.
The result (Fig. 9) indicated that the efficiency of
self-cleaning capability was higher in CAA cross-
link (95.59%) as compared with BTCA cross-link
(69.96%) under the UV irradiation for 60 minutes.
This finding is also in accordance with the previous
result by means qualitative test showing the cotton
fiber treated by CAA cross-link acquired a higher
degradation capability against malachite green as
compared with BTCA cross-link.
Fig. 9. The relationship curve of between UV radiation time
and degradation rate of malachite green (5.0 mg.L -1).
CONCLUSION
In this recent study, a self-cleaning textile
cotton fiber coated by TiO2/Chitosan/SiO2 nanocluster
was successfully developed. The TiO2/Chitosan/SiO2
morphologically depicted an anatase structure, with
13.1 mm of crystallite size and a band gap (Eg) =
3.20 eV. This particle acquired the self-cleaning
capability against malachite green dye under the
UV irradiation (λ = 365 nm; 536 Lux). The increase of
self- cleaning efficiency was determined by cross-link
 RILDA et al., Orient. J. Chem., Vol. 34(6), 2942-2947 (2018)
functionalization in consistent with the abundance of
TiO2/Chitosan/SiO2 coating on the cotton fiber. The
gradual cross-link functionalization using CAA could
highly optimize the self-cleaning efficiency (96.0%)
as compared with BTCA (69.96%). The functional
optimization of CAA was noticeably correlated with
the morphological features revealed by SEM, XRD,
and FT-IR analysis.
REFERENCES
1. Zhang, D.; Ling, C.; Chuanfeng, Z.; Yuyue, Z.;
Hong, L. J. Carbohydrate Polymer., 2013, 8,
2088-2094.
2. Shaban, M.; Semsem, A.; Ahmed, A.K. J.
Basic app. Sci., 2016, 5, 277-283.
3. Rilda, Y.; Fa d h l i ; S y u k r i ; A d m i n , A . ;
Hermansyah, A.; Sheela, C.; Hadi, N. J.
Technol. Eng., 2016, 78, 113-120.
4. Wijesena, R. N.; Nadeeka, D.T.; Rangana, P.;
Nalin, D.S.; Gehan, A. J. Molecular Catalysis
A., 2014, 398, 107-114.
5. Karimi, L.; Mirjalili, M.E.; Yazdanshenas, A.;
Nazari. J. Photochemistry and Photobiology.,
2010, 86, 1030-1037.
6. Deyong, W. J. Surface Coating Technol., 2009,
203, 3728-3733.
7. Pakdel; Esfandiar; Walid, A.; Daoudb; Xungai,
W. App. Surface Sci. Australian Future Fibres
Research and Innovation Centre, Institute
for Frontier Materials, Deakin University,
Australia., 2013, 275, 397-402.
8. Nazari, A.; Montazer. J. Carbohydrate
Polymers., 2011, 83, 1119-1127.
9. Clara, A.S. J. Sol-Gel Sci. Technol., 2015, 73,
118-126.
10. Balachandran, K. J. Spectrochim Acta A Mol
Biomol Spectrosc., 2014, 128, 468-474.
11. Meilert, K.T.; Laub, D; Kiwi, J. J. Molecular
catalysis., 2005, 237, 101-108.
View publication stats
2947
ACKNOWLEDGEMENT
The authors thank the Directorate of
Research and Social Services of the Ministry of
Research, Technology and Higher Education of
Indonesia for funding this research
(Competency-based Research Grant Scheme,the
fiscal year 2018) and also thank the division of
research and social services of Andalas University for
facilitating this grant.
12. Aksoy, Sennur, A. Cellulose Chem. Technol.
Textile Enginering Department Sileyman
Demirel University., 2013, 49, 405-413.
13. Zayyim, E. O. J. Material Sci., 2005, 40, 1345-
1352.
14. Li, W.; Xiahong, X., Siyao, C.; Xingping, Z.;
Lan, L.; Dajun, C.; Xiaqin, W. J. Carbohydrate
Polymers., 2008, 71, 574-58.
15. Jiang, R.; Zhu, H.; Chenc, J.; Yaoa, B.Y.Q.;
Fub, Z.Y.; Zhanga, Y.M.; Xu. App. Surface
Chem., 2014, 319, 189-196.
16. Galkina, O.L. J. Surface Coating Technol.,
2014, 253, 171-179.
17. Jiang, R.; Zhu, H. Y.; Chenc, H.; Yaoa, J.; Fub,
B. Y. Q.; Zhanga, Z. Y.; Xu, Y. M. App. Surface
Chem., 2014, 319, 189-196.
18. Rilda,Y.; Reza, S.; Anthoni, A.; Nasril, N.;
Achmad, S.; Hadi, N. J. Chin. Chem. Soc.,
2017, 64, 1347-1353.
19. Rilda, Y.; Admin, A.; Edison, M.; Baharuddin, S.;
Stefani, K. Asian J. Chem., 2015, 27, 3983-398.
20. Aziz; Radhiyah, A;. Iis, S. Department of
Manifacturing and Material Engineering
Faculty Engineering International Islamic
University Malaysia., 2009, 48 A, 951-957.
21. Junling, L. J. Physic. Chem. C., 2009, 112,
12412-12418.
22. Chen, C. C.; Lu, C. S.; Chung, Y. C.; Jan, J.
L. J. Hazardous Mat., 2007, 141, 520-528.